BS ISO 4939:2016

BSI Standards Publication

Steel — Determination of
nickel — Dimethylglyoxime
spectrophotometric method
BS ISO 4939:2016 BRITISH STANDARD

National foreword
This British Standard is the UK implementation of ISO 4939:2016.
It supersedes BS 6200-3.20.3:1985 which is withdrawn.
The UK participation in its preparation was entrusted to Technical
Committee ISE/102, Methods of Chemical Analysis for Iron and Steel.
A list of organizations represented on this committee can be
obtained on request to its secretary.
This publication does not purport to include all the necessary
provisions of a contract. Users are responsible for its correct
application.
© The British Standards Institution 2016.
Published by BSI Standards Limited 2016
ISBN 978 0 580 81536 2
ICS 77.080.01
Compliance with a British Standard cannot confer immunity from
legal obligations.
This British Standard was published under the authority of the
Standards Policy and Strategy Committee on 29 February 2016.
Amendments/corrigenda issued since publication
Date Text affected
 BS ISO 4939:2016

INTERNATIONAL ISO
STANDARD 4939

Second edition
2016-02-01

Steel — Determination of
nickel — Dimethylglyoxime
spectrophotometric method
Aciers — Détermination du nickel — Méthode spectrophotométrique
à la diméthylglyoxime

Reference number
ISO 4939:2016(E)

© ISO 2016
BS ISO 4939:2016
ISO 4939:2016(E)


COPYRIGHT PROTECTED DOCUMENT

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 BS ISO 4939:2016
ISO 4939:2016(E)


Contents Page

Foreword......................................................................................................................................................................................................................................... iv
1 Scope.................................................................................................................................................................................................................................. 1
2 Normative references....................................................................................................................................................................................... 1
3 Principle......................................................................................................................................................................................................................... 1
4 Reagents......................................................................................................................................................................................................................... 1
5 Apparatus...................................................................................................................................................................................................................... 2
6 Sampling......................................................................................................................................................................................................................... 2
7 Procedure..................................................................................................................................................................................................................... 2
7.1 Test portion................................................................................................................................................................................................. 2
7.2 Blank test...................................................................................................................................................................................................... 2
7.3 Determination.......................................................................................................................................................................................... 2
7.3.1 Preparation of the test solution........................................................................................................................... 2
7.3.2 Colour development....................................................................................................................................................... 3
7.3.3 Preparation of the compensating solution................................................................................................. 3
7.3.4 Spectrophotometric measurement................................................................................................................... 3
7.4 Establishment of the calibration curve............................................................................................................................... 3
7.4.1 Preparation of the calibration solutions....................................................................................................... 3
7.4.2 Spectrophotometric measurement................................................................................................................... 4
7.4.3 Calibration curves........................................................................................................................................................... 4
8 Expression of results......................................................................................................................................................................................... 4
9 Precision........................................................................................................................................................................................................................ 5
9.1 General............................................................................................................................................................................................................ 5
9.2 Repeatability.............................................................................................................................................................................................. 5
9.3 Reproducibility........................................................................................................................................................................................ 5
10 Test report.................................................................................................................................................................................................................... 5
Annex A (informative) Additional information on the international interlaboratory test.......................... 7
Annex B (informative) Graphical representation of precision data..................................................................................... 8
Bibliography................................................................................................................................................................................................................................. 9

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BS ISO 4939:2016
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Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www.iso.org/patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the meaning of ISO specific terms and expressions related to conformity
assessment, as well as information about ISO’s adherence to the WTO principles in the Technical
Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information.
The committee responsible for this document is ISO/TC 17, Steel, Subcommittee SC 1, Methods of
determination of chemical compound.
This second edition cancels and replaces the first edition (ISO 4939:1984), which has been
technically revised. In particular, the specification of plotting of the calibration graphs shown in
7.4.3 has been corrected.

iv  © ISO 2016 – All rights reserved

 BS ISO 4939:2016
INTERNATIONAL STANDARD ISO 4939:2016(E)

Steel — Determination of nickel — Dimethylglyoxime

spectrophotometric method

1 Scope
This International Standard specifies a spectrophotometric method for the determination of nickel in
steel using dimethylglyoxime.
The method is applicable to the determination of nickel mass fractions in the range of 0,10 % and 2,0 %.
Cobalt, copper and manganese can cause interferences (see 7.3.2).

2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
ISO 648, Laboratory glassware — Single-volume pipettes
ISO 1042, Laboratory glassware — One-mark volumetric flasks
ISO 3696, Water for analytical laboratory use — Specification and test methods
ISO 14284, Steel and iron — Sampling and preparation of samples for the determination of chemical
composition

3 Principle
Dissolution of a test portion in hydrochloric, nitric and perchloric acids.
Formation of a coloured complex of nickel(lll) with dimethylglyoxime in ammoniacal solution containing
iodine and potassium iodide.
Spectrophotometric measurement at a wavelength of about 535 nm.

4 Reagents
During the analysis, unless otherwise stated, use only reagents of recognized analytical grade and only
grade 2 water as specified in ISO 3696.

4.1 Acid mixture.

Mix two volumes of hydrochloric acid, ρ approximately 1,19 g/ml, one volume of nitric acid, ρ
approximately 1,40 g/ml and two volumes of water.

4.2 Perchloric acid, ρ approximately 1,54 g/ml.

WARNING — Perchloric acid vapour might cause explosions in the presence of ammonia, nitrous
fumes or organic material in general.
Perchloric acid, ρ approximately 1,67 g/ml, may also be used. 100 ml of perchloric acid, ρ approximately
1,54 g/ml is equivalent to 79 ml of perchloric acid, ρ approximately 1,67 g/ml.

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ISO 4939:2016(E)


4.3 Ammonium citrate, 250 g/l solution.

Dissolve 250 g of citric acid monohydrate (C6H8O7·H2O) in 250 ml of ammonia solution, ρ approximately
0,91 g/ml, cool, dilute to 1 l with water and mix.

4.4 Iodine, 12,7 g/l solution.

Dissolve 25 g of potassium iodide and 12,7 g of iodine in the minimum volume of water. Dilute to 1 l
with water and mix.

4.5 Dimethylglyoxime, 1 g/l solution.

Dissolve 1 g of dimethylglyoxime in 500 ml of ammonia solution, ρ approximately 0,91 g/ml, dilute to 1 l

with water and mix.

4.6 Ammonia solution, ρ approximately 0,91 g/ml, diluted 1 + 1.

4.7 Nickel standard solution, 0,5 g/l.

Weigh, to the nearest 0,001 g, 0,500 g of high purity nickel [purity > 99,95 % (mass fraction)] and
dissolve in 20 ml of nitric acid, ρ approximately 1,40 g/ml, diluted 2 + 3. Heat to boiling to remove
nitrous fumes. Cool and transfer the solution quantitatively to a 1 000 ml one-mark volumetric flask,
dilute to the mark with water and mix.
1 ml of this standard solution contains 0,5 mg of nickel.

5 Apparatus
All volumetric glassware shall be Class A, in accordance with ISO 648 and ISO 1042.
Ordinary laboratory apparatus and the following shall be used.
Spectrophotometer, suitable for measuring the absorbance of the solution at a wavelength of 535 nm
with cells of 1 cm or 4 cm optical path length.

6 Sampling
Carry out sampling in accordance with ISO 14284 or appropriate national standards for steel.

7 Procedure

7.1 Test portion

Weigh, to the nearest 0,001 g, approximately 0,5 g of the test sample.

7.2 Blank test

In parallel with the determination and following the same procedure, carry out a blank test using the
same quantities of all the reagents except the test portion.

7.3 Determination

7.3.1 Preparation of the test solution

Introduce the test portion (7.1) into a 250 ml beaker. Add 10 ml of acid mixture (4.1) and 10 ml of
perchloric acid (4.2). Cover the beaker with a watch-glass and heat until acids action ceases.

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Evaporate until white fumes of perchloric acid appear and continue fuming at a temperature suitable to
maintain a steady reflux of perchloric acid fumes on the walls of the beaker for at least 3 min and until
any chromium is oxidized to chromate. Remove from the source of heat and allow to cool.
Add 50 ml of water, heat to dissolve salts, cool and transfer quantitatively to a 250 ml one-mark
volumetric flask. Dilute to the mark with water and mix.
Filter by decantation through a dry filter to remove any residue or precipitate and collect the filtrate in
a dry beaker, discarding the first fractions of the filtrate.

7.3.2 Colour development

Transfer a 25 ml aliquot portion of the test solution (7.3.1) to a 100 ml one-mark volumetric flask.
If the test solution (7.3.1) contains cobalt, copper or manganese, the aliquot portion taken should be
such that the respective contents of these elements do not exceed the following limits: cobalt, 5 mg;
copper, 0,5 mg; manganese, 1 mg.
Add 20 ml of the ammonium citrate solution (4.3), mix, then add 3 ml of the iodine solution (4.4) and
mix again. Allow to stand for 5 min.
Add 20 ml of the dimethylglyoxime solution (4.5), dilute to the mark with water and mix.
Allow to stand for at least 10 min and at most 20 min at a temperature of 20 °C ± 5 °C.

7.3.3 Preparation of the compensating solution

Transfer a 25 ml aliquot portion of the test solution (7.3.1) to another 100 ml volumetric flask.
Add 20 ml of the ammonium citrate solution (4.3), mix, then add 3 ml of the iodine solution (4.4) and
mix again. Allow to stand for 5 min.
Add 20 ml of the ammonia solution (4.6), dilute to the mark with water and mix.
Allow to stand for at least 10 min and at most 20 min at a temperature of 20 °C ± 5 °C.

7.3.4 Spectrophotometric measurement

Carry out the spectrophotometric measurement of the test solution at a wavelength of about 535 nm
in a cell of appropriate optical path length (1 cm or 4 cm) after having adjusted the spectrophotometer
(Clause 5) to zero absorbance with the corresponding compensating solution (7.3.3).

7.4 Establishment of the calibration curve

7.4.1 Preparation of the calibration solutions

Introduce into a series of 250 ml beakers containing 10 ml of the acid mixture (4.1) and 10 ml of
perchloric acid (4.2), the volumes of the nickel standard solution (4.7) indicated in Table 1, as appropriate
for the expected nickel content.
Treat as described in 7.3.1 and 7.3.2, using the calibration solution “0” as the compensating solution.

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BS ISO 4939:2016
ISO 4939:2016(E)


Table 1 — Composition of the calibration solutions and cell optical path length
Nickel
concentration in
Nickel standard Cell optical
Nickel content the solution for
solution (4.7) path length
spectrophotometric
% (mass fraction)
ml measurement cm
μg/ml
0 0
1,0 0,5
2,0 1,0
0,1 to 0,5 4
3,0 1,5
4,0 2,0
5,0 2,5
0 0
4,0 2,0
6,0 3,0
8,0 4,0
0,5 to 2,0 1
10,0 5,0
14,0 7,0
16,0 8,0
20,0 10,0

7.4.2 Spectrophotometric measurement

Carry out spectrophotometric measurements of each solution at a wavelength of about 535 nm after
having adjusted the spectrophotometer (Clause 5) to zero absorbance with the calibration solution “0”
(7.4.1) used as the compensating solution.

7.4.3 Calibration curves

For each range of nickel content and appropriate optical path length of the cells (see Table 1),
establish the corresponding calibration graph by plotting the net absorbance values against the nickel
concentrations, expressed in micrograms per millilitre, in the calibration solutions.

8 Expression of results
Convert the absorbance (7.3.4) into the corresponding concentration, expressed in micrograms of
nickel per millilitre, in the colour-developed test solution by using the calibration curve (7.4.3).
The nickel content (CNi), expressed as a (%) mass fraction, is given by Formula (1), Formula (2) and
Formula (3):

V0 Vt
C Ni = ( ρ Ni1 − ρ Ni0 ) ×
1
× × × 100 (1)
10 6 V1 m

C Ni = ( ρ Ni1 − ρ Ni0 ) ×
1 250 100
× × × 100 (2)
10 6 25 m

C Ni = ( ρ Ni1 − ρ Ni0 ) ×
1
(3)
10m
where

m is the mass of the test portion (7.1), in grams;

V0 is the volume of the test solution (7.3.1), in millilitres;

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V1 is the volume of the aliquot portion (7.3.2), in millilitres,;

Vt is the volume of the colour-developed test solution (7.3.2), in millilitres;

ρNi0 is the concentration of nickel in the blank test solution (corrected for its compensating
solution), expressed in micrograms per millilitre;

ρNi1 is the concentration of nickel in the test solution (corrected for its compensating solution),
expressed in micrograms per millilitre.

9 Precision

9.1 General
A planned trial of this method was carried out by five laboratories, at six levels of nickel, each laboratory
making six determinations of nickel at each level.
The results obtained were treated statistically in accordance with ISO 5725:1986[1].
The obtained data showed a logarithmic relationship between nickel content and repeatability and
reproducibility of the test results. Table 2 shows the smoothed data derived from these relationships.
The graphic presentation of the precision data is given in Annex B.

Table 2 — Repeatability and reproducibility limits

Nickel content Repeatability limit Reproducibility limit
% (mass fraction) r R
0,1 0,010 0,013
0,2 0,013 0,018
0,5 0,019 0,027
1,0 0,025 0,038
2,0 0,034 0,053

9.2 Repeatability
The difference between two single and independent results obtained on identical test material by one
analyst using the same apparatus within a short time interval in the normal and correct operation of
the test method will exceed the repeatability, r, only in one case in 20 cases.

9.3 Reproducibility
The difference between two single and independent results obtained by two operators working in
different laboratories on identical test material in the normal and correct operation of the test method
will exceed the reproducibility, R, only in one case in 20 cases.

10 Test report
The test report shall include the following information:
a) all information necessary for the identification of the sample, the laboratory and the date of analysis;
b) method used by reference to this International Standard, i.e. ISO 4939;
c) results and unit in which they are expressed;
d) any unusual features noted during the determination;

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BS ISO 4939:2016
ISO 4939:2016(E)


e) any operation not specified in this International Standard or any optional operation which might
have influenced the results.

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 BS ISO 4939:2016
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Annex A
(informative)

Additional information on the international interlaboratory test

Table 2 has been derived from the results of the international trial carried out in 1979 on six steel
samples in two countries involving five laboratories.
The results of the trials were reported in document 17/1 N 433, November 1980.
The test samples used are shown in Table A.1.

Table A.1 — Test samples

Nickel content
Sample % (mass fraction)
Certified Found
BCS 260/4 (high purity iron) 0,003 0,005 5
BCS 431 (plain carbon steel) 0,069 0,066 4
BCS 341 (24 % Cr stainless steel) 0,56 0,556
BCS 226/2 (Ni-Cr-Mo steel) 1,43 1,434
BCS 406 (low alloy steel) 1,69 1,690
BCS 410 (low alloy steel) 2,04 2,034

NOTE 1 The statistical analysis was performed in accordance with ISO 5725:1986[1].

NOTE 2 Six samples were used for the international interlaboratory test. However, as the method is applicable
to nickel mass fraction between 0,10 % and 2,0 %, only five points have been illustrated on the figure in Annex B,
the data for sample BCS 260/4 (Ni mass fraction: 0,003 %) have been omitted.

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BS ISO 4939:2016
ISO 4939:2016(E)


Annex B
(informative)

Graphical representation of precision data

0,1
r(%)
Y R(%)
r
0,01 R

0,001
0,01 0,1 1 10
X

Key
X nickel content, % (mass fraction)
Y precision, % (mass fraction)
lg r =0,407 9 lg WNi - 1,597
lg R =0,4677 lg WNi - 1,420

Figure B.1 — Logarithmic relationship between nickel content (wNi) and repeatability (r) and
reproducibility (R)

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 BS ISO 4939:2016
ISO 4939:2016(E)


Bibliography

[1] ISO 5725:1986,1)Precision of test methods — Determination of repeatability and reproducibility for
a standard test method by inter-laboratory tests

1) Withdrawn. (Replaced with the ISO 5725 series.)

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BS ISO 4939:2016
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